Silyl organometallocenes useful as antioxidants

ABSTRACT

SILYLORGANOMETALLOCENES SELECTED FROM THE CLASS OF (A) POLYMERS OF THE FORMULA,   (C5Q5)M(C5Q4)-CO-NH-R&#34;-SI(-(R)A)-O((3-A)/2)   (B) COPOLYMERS HAVING UNITS OF THE FORMULA,   (R)B-SI-O((4-B)/2)   AND AT LEAST ONE UNIT OF (A), AND (C) DISILOXANES OF THE FORMULA,   ((C5Q6)M(C5Q4)-CO-NH-R&#34;-SI(-R)2)2-O   WHERE R IS A MONOVALENT HYDROCARBON RADICAL, R&#34; IS A DIVALENT HYDROCARBON RADICAL, AND(C5Q4)M(C5Q5) IS AN ORGANOMETALLOCENE, WHERE Q IS SELECTED FROM HYDROGEN, AN ELECTRON DONATING ORGANIC RADICAL, AND AN ELECTRON WITHDRAWING ORGANIC RADICAL AND M IS A TRANSITION METAL, A IS A WHOLE NUMBER EQUAL FROM 0 TO 2 AND B IS A WHOLE NUMBER EQUAL FROM 0 TO 3. THESE SILYLORGANOMETALLOCENES ARE USEFUL AS ANTIOXIDANTS FOR ORGANOPOLYSILOXANE FLUIDS UNDER EXTREME OXIDATION CONDITIONS.

United States Patent O ABSTRACT on THE DISCLOSUREsilylorganometallocenes selected from the class of (a) polymers of theformula,

H h tQs) sQ4) NR"SiO 2 (b) copolymers having units of the formula,

( SiO and at least one unit of (a), and (c) disiloxanes of the formula,

. H V BQ SQ4) -N-[R-"(RhSihO where R is a monovalent hydrocarbonradical, R is a divalent hydrocarbon radical, and (C Q M(C Q is anorganometallocene, where Q is selected from hydrogen, an electrondonating organic radical, and an electron withdrawing organic radicaland M is a transition metal, a is a whole number equal from 0 to 2 and bis a whole number equal from 0 to 3. These silylorganometallocenes areuseful as antioxidants for organopolysiloxane fluids under extremeoxidation conditions.

BACKGROUND OF THE INVENTION The present inventionrelates toorganopolysiloxanes and particularly to organopolysiloxanes having anorganometallocene radical attached to the silicon by a carbonsiliconlinkage.

silylorganometallocenes can be made into room temperature vulcanizablerubbers having superior oil reversion resistance. Further,silylorganometallocenes can be utilized in smoke eliminators, dyestulfs,photographic developers, rubber vlucanization accelerators, diesel fueladditive, metal-plating reagents, polymerization catalysts, medicines,fungicides, pesticides, agricultural chemicals, damping fluids andmetallocene-containing vinyl monomers for polymerization as such, orwith other monomers such as chloroprene and styrene.

Recently, automobiles have been manufactured with a variable speed fan.The fan is connected to the crankshaft of the motor by means of a fluidclutch. During low operating temperatures, as when the auto is idling,little fluid is passed to the fluid clutch so that there is slipping inthe clutch so that the drive shaft of the fan is not driven at the truespeed of the crankshaft. When the temperature of the motor rises, athermostat opens up to allow fluid into the fluid clutch sothat theshaft of the fan is rotated at the speed of the crankshaft. In order tooperate such a fluid clutch, it is necessary to utilize in it a fluidthat is capable of withstanding high torsional forces at hightemperatures without breaking down by oxidizing and gelling. For such anapplication dimethylpolysiloxane fluid has been found especiallysuitable. However, this fluid oxidizes at high temperatures above 200 C.after continued use 'icev in such fluid clutch for 50 hours or more.Various antioxidants were added to the polysiloxane fluid to prevent itsoxidation and gelling. Examples of such antioxidants are iron oxide,iron octoate, and manganese oxide. However, with all such antioxidantsthe compound either precipitated out of the fan clutch fluid or did notsufficiently protect the polysiloxane fluid and, in particular,dimethylpolysiloxane, from oxidizing and gelling. None of theseantioxidants were able to prevent polysiloxane fluids from oxidizingafter operating in the clutch continuously for 200 hours.

It is one object of this invention to provide a novel class ofsilylorganometallocenes having unique properties.

It is another object to provide a class of silylorganometallocenes whichcan stabilize and prevent polysiloxane fluids from oxidation.

7 It is yet another aim to provide a method for producing a novel classof silylorganometallocenes.

These and other objects are accomplished by the present invention setforth below.

SUMMARY OF THE INVENTION (b) Copolymers composed of structural units ofthe formula,

and at least one unit of (a),

(c) Disiloxanes of the formula,

where R is a member selected from the class consisting of monovalenthydrocarbon radicals, halogenated monovalent hydrocarbon radicals, cyanoradicals and fluoroalkyl radicals, S is an organometallocene radicalhaving the formula,

where W is a carbamyl radical, R" is selected from the class consistingof an arylene radical and an alkylene radical, Q is chemically bonded toa cyclopentadienyl radical and is a member selected from the classconsisting of hydrogen, a monovalent electron donating organic radicaland a monovalent electron withdrawing organic radical and M is atransition metal bonded to cyclopentadienyl radicals. In the aboveformula, a is a whole number equal from 0 to 2, and b is a whole numberequal from 0 to'3.

There is further provided by the present invention a process forpreventing the decomposition of polysiloxane fluids by mixing into thefluids an effective amount of the above silylorganometallocenes.

BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENT Radicals included by Rare, for example, mononuclear and binuclear aryl and aralkyl, such asphenyl,'naphthyl, benzyl, tolyl, xylyl, 2,6-di-t-butylphenyl,4-butylphenyl, 2,4,6-trimethylphenyl, biphenyl and ethylphenyl;halogensubstituted mononuclear and binuclear aryl, such as 2,6-dichlorophenyl, 4-bromophenyl, 2,5-di-fluorophenyl, 4,4-dichlorobi-phenyl, 2'-chloronaphtyl, 2,4,6-trichlorophenyl and2,5-dibromopheny1; nitro-substituted mononuclear and binuclear aryl,such as 4-nitrophenyl and 2,6-di-nitrophenyl; alkoxy-substituted monoand binuclear aryl, such as 4-methoxyphenyl, 2,6-dimethoxyphenyl,4-t-butoxyphenyl, 2-ethoxyphenyl, 2-ethoxynaphthyl and2,4,6-trimethoxyphenyl; alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl, hexyl,heptyl, octyl, nonyl, decyl and dodecyl; alkenyl such as vinyl, allyl,n-butenyl-l, n-butenyl-Z, n-pentenyl-Z, nhexenyl-Z,2,3-dimethylbutenyl-2, n-heptenyl, n-decenyl and n-dodecenyl; alkynylsuch as propargyl and 2- butynyl; haloalkyl such as chloromethyl,iodomethyl, bromomethyl, fluoromethyl, chloroethyl, iodoethyl,bromoethyl, fluoroethyl, trichloromethyl, diiodoethyl, tribromomethyl,trifiuoromethyl, dichloroethyl, chloro-npropyl, bromo-n-propyl,iodoisopropyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3 trichlorobutyl,1,3,3 tribromobutyl, chloropentyl, bromopentyl, 2,3-dichloropentyl, 3,3-dibromopentyl, chlorohexyl, bromohexyl, 2,4-dichlorohexyl,1,3-dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl,fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl,2,4-dichloromethylheptyl, chlorooctyl, bromooctyl, iodooctyl,2,4-dichloromethylhexyl, 2,4- dichlorooctyl, 2,4,4-trichloromethylpentyland 1,3,5-tribromooctyl; haloalkenyl such as chlorovinyl, bromovinyl,chloroallyl, bromoallyl, 3-chloro-n-butenyl-l, 3-chloro n-pentenyl-l,3-fiuoro-n-heptenyl-l, 1,3,3-trichloro-n-heptenyl-S,1,3,S-trichloro-n-octenyl-G, and 2,3,3-trichloromethylpentenyl-4;haloalkynyl such as chloropropargyl and bromopropargyl; nitroalkyl suchas nitromethyl, nitroethyl, nitro-n-propyl, nitro-n-butyl, nitropentyland 1,3-dinitroheptyl; nitroalkenyl such as nitroallyl,3-nitron-butenyl-l, and 3-nitro-n-heptenyl-1; nitroalkynyl such asnitropropargyl; alkoxyalkyl and polyalkoxyalkyl such as methoxymethyl,ethoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl,ethoxyethoxyethyl, methoxyethoxymethyl, butoxymethoxyethyl,ethoxybutoxyethyl, me-

thoxy-propyl, butoxypropyl, methoxybutyl, butoxybutyl, methoxypentyl,butoxypentyl, methoxymethoxypentyl, butoxyhexyl, methoxyheptyl andethoxyethoxy; alkoxyalkenyl and polyalkoxylkenyl such as ethoxyvinyl,methoxyallyl, butoxyallyl, ethoxy n butenyl l, butoxy n pentenyl-l andmethoxyethoxy n heptenyl-l; alkoxyalkynyl and polyalkoxyalkynyl such asmethoxypropargyl; cycloalkyl, cycloalkenyl and alkyl, halogen, alkoxyand nitro-substituted cycloalkyl and cycloalkenyl such as cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, 6-methylcyclohexyl,2,5-dimethylcycloheptyl, 4-butylcyclopentyl, 3,4-dichlorocyclohexyl, 2,6dibromocycloheptyl, 6 methoxycyclooctyl, Z-nitrocyclopentyl,Z-cyclopentenyl, 3-methyl-l-cyclopentenyl, 5- methoxy l-cyclopentenyl,3,4-dimethyl-l-cyclopentenyl, 2,5 dimethoxy l cyclopentenyl, Smethyl-S-cyclopentenyl, 3,4 dichloro S cyclopentenyl, 5-(tert-butyl)- 1cyclopentenyl, 2-nitrol-cyclohexenyl, l-cyclohexenyl, 3 methyll-cyclohexenyl, 3,4-dimethyl-l-cyclohexenyl and6-methoxy-l-cyclohexenyl; cyanoalkyl such as cyanomethyl, cyanoethyl,cyanobutyl and cyanoisobutyl; cyano radicals; and fiuoroalkyl.

Radicals included by R" are arylene radicals and alkylene radicals suchas phenylene, tolylene, methylene, ethylene, propylene, trimethylene,tetramethylene, pentamethylene and decamethylene.

W is a divalent carbamyl radical having the formula Unless otherwisedesignated, the term metallocene" as employed in the description of thepresent invention is an organometallic compound of a transistion metalchemically combined with two five-membered carboxylics substituted witheither hydrogen, or a mixture of hydrogen and either monovalent electrondonating radicals or monovalent electron withdrawing radicals ormixtures thereof.

With reference to the monovalent electron donating organic radicalsencompassed by Q, there are aryl radicals and hydroxyaryl, for example,phenyl, tolyl and hydroxyphenyl; aliphatic radicals including allylradicals such as methyl, ethyl, propyl, butyl and octyl; alkoxy radicalssuch as vinyl and propargyl; cycloaliphatic such as cyclohexyl andcycloheptyl; carboxyaliphatic radicals such as carboxymethyl, andcarboxyethyl; triorganosilyl radicals such as trimethylsilyl anddimethylphenylsilyl; nitro-aliphatic radicals such as nitromethyl andnitroethyl. The symbol Q also encompasses monovalent electronwithdrawing organic radicals such as aliphatic aryl, formyl, acetyl,propionyl, arylaryl such as benzoyl; carboxy; aldehydic; sulfo;carboxyaryl, for example, carboxyphenyl and carboxylyl; nitroaryl, forexample, nitrophenyl; haloaryl, for example, chlorophenyl andbromotolyl; and haloaliphatic such as chloromethyl and chloroethyl.Radicals included by R of Formulas 1, 2 and 3 can be all the sameradicals or any two or more of the aforementioned R radicals. Similar,radicals included by Q can be all the same radicals or any two or moreof the aforementioned Q radicals.

Transition metal utilized in the description of the present inventionshown by M of Formula 4 includes all metals of Group 'III to VIII of thePeriodic Table capable of forming a 11' complex with a cyclopentadienylradical to form a metallocene. The transition metals that are operativein the present invention are, for example, metals having atomic numbers22 to 28, 40 to 46, and 71 to 78, such as titanium, vanadium, chromium,manganese, iron, cobalt, nickel, zirconium, columbium, molybdenum,technetium, ruthenium, rhodium, palladium, hafnium, tantalum, tungsten,rhenium, osmium, iridium and platmum.

The organopolysiloxanes of the present invention are produced byhydrolyzing metallocenyl halides of the formula,

sWR"siX where S, W, R", R and a are as defined above and X is a halogenradical. The copolymeric organopolysiloxanes are produced bycohydrolyzing the metallocenyl halide of formula 5 with halosilanes ofthe formula,

s iXr-b where R and b are as defined above and X is a halogen radical.

The disiloxane of Formula 3 is produced by hydrolyzing a metallocenylhalide of the formula,

SWR-SiX Where S, W, R", R and X are as defined above.

The metallocenyl halides of Formulas 5 and 7 are prepared by reacting ametallocene having the formula,

with a silyl isocyanate halide of the formulas,

where M, R, R, X and a are as defined previously, Q is an electrondonating radical, Q is an electron withdrawing radical, c is an integerequal from 1 to 5, d is a whole number equal from 0 to 4 and e is awhole number equal from 0 to 1, while the sum of c, d and e is equal to5. The reaction is a modified Friedel-Crafts reaction and is carried outin the presence of a Lewis acid such as boron trifluoride, phosphoricacid, hydrogen fluoride, zinc chloride, stannic chloride and aluminumchloride, which is preferred. Molar amounts of the reactants are used tocarry out the reaction under preferred conditions. The reaction ispreferably carried out in a chlorinated hydrocarbon solvent such aschloroform, dichloromethane, dichloroethane, etc. Other suitablesolvents are benzene, nitrobenzene and carbon disulfide. Thetemperature, at which the reaction can be carried out varies widely, forinstance a temperature range of 25 C. to 100 C. has been found operable,while a range of to 25 C. is preferred.

The addition reaction can be carried out by any of several well knownFriedel-Crafts procedures. One method, for'example, involves forming acomplex of the halosilyl isocyanate and of the Friedel-Crafts catalystand then reacting the complex with the metallocene in solvent.Variations of the procedures can also be carried out. For example, thehalosilyl isocyanate can be added to a mixture of the aluminum halideand the metallocene in solvent.

The reaction products of metallocenyl silyl halide of Formulas and 7 maybe hydrolyzed by standard procedure. For the hydrolysis, an acidifiedmixture of water and ice can be employed. The final product can beextracted by use of a suitable organic solvent, and then removed inaccordance with standard procedures, such as chromatography.

The halosilyl isocyanate of Formulae 9 and 10 are prepared by reacting ahalosilane of the formula,

where R is as previously defined, R is a divalent hydrocarbon radicalsuch as alkylene or arylene radical, g is a Whole number from 0 to 3,and n is any whole number including 0. The reaction is preferablycarried out without'a solvent. In order for the reaction to proceed, aplatinum catalyst must be used. Preferably platinum on a metal supportor solubilized platinum is used. Examples of suitable platinum catalystsare disclosed in US. Pat. 3,220,972. Other suitable platinum catalystsare olefin platinum complexes, alcohol platinum complexes,chloroplatinic acid and platinum on solid supports as y-alumina orcharcoal. The reaction is preferably carried out at a temperature in therange of 50100 C. The resulting halosilyl isocyanates are purified bystandard procedures.

The halosilyl isocyanates of Formulas 9 and 10 may also be reacted withhydrogen chlorides to yield halosilyl carbamyl halides which can thus beused to acylate an organometallocene nucleus to yield the halosilylmetallocenes of Formulas 5 and 7. The acylating reaction is amplydescribed in detail in US. Pat. 3,321,501 assigned to the same assigneeas the present case.

If it is desired that W in Formulas 5 and 7 be a carbonyl group insteadof a carbamyl group, then by the hydrolysis of NOR/'Si O which can beprepared by Pt catalyzed hydrosilyation of olefin nitriles as allylcyanide a compound of the formula,

is obtained. The disiloxane of Formula 13 is then reacted with aninorganic acid halide such as PX PX SOX BX where X is a halogen radicalto yield a halosilylcarbonyl halide which can then be used to acylate anorganometallocene to produce a halide of Formula 7 when W is carbonyLThecarbonyl radical may further be modified or removed by a Chemminsreaction. The halosilylacylmetallocene of Formula 7 is hydrolyzed andthen reaction with zinc am algam in the presence of HCl to yield thecorresponding saturated alkane.

Further, the acylated metallocene of Formulas 5 and 7 when W is acarbonyl group can be modified by converting the carbonyl group inaccordance with standard chemical procedures to anothercarbo-functionalgroup. Further, modification of' the metallocene nucleus can also beachieved such as by alkylation, sulfonation, and other standardreactions analogous to chemical reactions common to organic aromaticchemistry. In addition, the monovalent functional groups on the siliconatoms of the silylorgano radical can also be replaced with othermonovalent radicals to provide for additional chemical reactions withthe halosilylmetallocene. For example, .a silicon-carbon cleavagereaction can be utilized to form silanol radicals and silicon-halogenbonds which can be alkoxylated to form alkoxy silicones.

Some of the silylorganometallocenes of the present invention that can bemade directly from ferrocene, osmocene and ruthenocene as shown inFormula 4 are, for example,

trichlorosilylpropionylferrocene trimethylsilylpropionylosmocenetrimethylsilylpropionylruthenocene dimethylphenylsilylpropionylferrocenedimethylhydroxysilylpropionylosmocenedimethylhydroxysilylpropionylferrocenetrichlorosilylpropionylruthenocene dimethylchlorosilylpro ionylferrocenetrimethylsilylbenzoylruthenocene trimethylsilylphenylmethyleneosmocenedimethylsilyltetramethyleneferrocenemethyldiphenylsilyltetramethyleneosmocene2-hydroxy-4-trimethylsilylbenzoylferrocene Silylorganometallocenes ofthe present invention within the scope of Formulas 1 and 3 are:

N- (trimethylsilylpropyl)carbamylferrocene1,3-bis(ferrocenoylaminopropyl)tetramethyldisiloxanetetra(ferrocenoylaminopropyl)tetramethylcyclotetrasiloxaneN-(dimethylphenylsilylbutyl)carbamylosmocene N- trimethylsilylphenyl)carb amylruthenocene ferrocenoylaminobutylpolysiloxanea,w-ferrocenoylaminopropyldimethylsilyl (polydimethylsiloxane) 1,3-bis(osmocenoylaminopropyl)tetramethyldisiloxane1,3-bis(ruthenocenoylaminopropyl)tetramethyldisiloxane Organohalosilanesshown by Formulas 6 and 11 are well known and are shown in Rochow,Chemistry of the Silicones, 2nd edition, John Wiley & Sons (1151). Someof these Organohalosilanes are, for example, methyltrichlorosilane,dimethyldichlorosilane, methylphenyldichlorosilane,trimethylchlorosilane, etc.

The silylorganometallocenes of the present invention are very eflectiveantioxidants at high temperatures for polysiloxane fluids, such asdimethylpolysiloxane fluids. Other silylorganometallocenes, such asthose disclosed in Wilkus et al., US. Pat. 3,326,952, Wilkus et al., US.Pat. 3,321,501 and Wilkus et al., US. Pat. 3,324,157 are alsoantioxidants for polysiloxane fluids. However, they are not effectivehigh temperature antioxidants and were not able to pass the standardfluid clutch test as set forth in the examples below. Only the silylcarbamylorganometallocenes passed the fluid clutch test While thesilylcarbonylorganometallocenes did not prevent the polysiloxane fluidfrom disintegrating and gelling prior to the termination of the testperiod.

The silylcarbamylorganometallocenes of the present invention are simplymixed with the polysiloxane fluid it is desired to stabilize againstoxidation. Generally, 0.05- 1.0 percent by weight of the silylcarbamylorganometallm cene is used in the polysiloxane fluid andpreferably 0.1 to 0.8 percent by weight. If less than 0.05 percent byweight is used, then the polysiloxane fluid is not protected fromoxidation. If more than 1.00 percent by weight is used,

then there is an unnecessary usage of silylorganometallocene materials.

In order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustrationand not by way of limitation. All parts are by weight unless specifiedotherwise.

EXAMPLE 1 Into a S-necked flask equipped with a magnetic agitator,thermometer, condenser and maintained under a nitrogen atmosphere therewas added 9.4 parts (0.05 mole) of ferrocene and 100 ml. of dry ethylenechloride. After agitation had begun, there was added immediately 8.8parts (0.05 mole) of chlorodimethylsilylpropylisocyanate. The reactionmixture was then heated at a temperature in the range of 15 to 90 C. andthere was added over a two hour period 6.7 parts 0.05 mole) of anhydrousaluminum chloride. A blood red complex was formed. The reaction was keptat reflux for 48 hours.

At the end of that period the flask was cooled and the contents pouredover ice. The deep blue aqueous phase Was separated from the red organicphase, then the aqueous phase was washed with methylene chloride and thewashings combined with the organic phase. The organic phase was dried,stripped of solvent and then chromatographed. The resulting product waseluted with ethanol and purified by crystallization from ether-benzene.The product was obtained in 82% yield as yellow solid with M.P. of156-158 C. and having the structure:

The elemental analysis of the product as found and as calculatedtheoretically is set forth below:

Found (percent): Fe, 16.42; N. 4.18; Si, 8.52; C, 56.54; and H, 6.70.Theoretical (percent): Fe, 16.56; N, 4.15; Si, 8.33; C, 56.97; and H,6.87.

EXAMPLE 2 Using the same equipment as the previous example, 3.2 parts(0.1 mole) of osmocene is added to 50 ml. of dry ethylene chloride.Agitation is begun and immediately there is added 1.8 parts (0.1 mole)of chlorodimethylsilylpropylisocyanate. The reaction mixture is thenheated at a temperature in the range of 80 to 90 C. and there is addedover a two hour period 1.3 parts (0.01 mole) of anhydrous aluminumchloride at which point a colored complex was formed. The reaction iskept at reflux for at least 48 hours. At the end of this period theflask is washed and the contents poured over ice. The aqueous phase wasseparated from the organic phase. Then the aqueous phase is washed withmethylene chloride and the washings combined with the organic phase. Theorganic phase is dried, stripped of solvent and then chromotographed.The resulting product is eluted with ethanol and purified bycrystallization from ether-benzene. The product is obtained in 78% yieldas a solid having the structure:

on, H o (sr-c1nc1ncm-tflc'ounowmn) 11: 2 Infrared analysis and nuclearmagnetic resonance spectra confirmed this structure.

EXAMPLE 3 Using the same equipment as in the previous example, 2.3 parts(0.01 mole) of ruthenocene is added to 100 ml. of dry ethylene chloride.Agitation is begun and immediately there was added 1.8 parts (0.01 mole)of chlorodimethylsilylpropylisocyanate. The reaction mixture is thenheated at temperatures in the range of 75 -85 C. and there is added overa two hour period 1.3 parts (0.01 mole) of anhydrous aluminum chlorideat which point a 8 colored complex was formed. The reaction is kept atreflux for at least 50 hours. At the end of this period the flask wascooled and the contents poured over ice. The aqueous phase is separatedfrom the organic phase. Then the aqueous phase was washed with methylenechloride and the washings combined with the organic phase. The organicphase was dried, stripped of solvent and then chromatographed. Theresulting product is eluted with ethanol and purified by crystallizationfrom ether-benzene. The product was obtained in yield having thestructure:

OH; H fl) infrared analysis and nuclear magnetic resonance spectraconfirmed this structure.

EXAMPLE 4 Example 1 is repeated but before the hydrolysis stage isinitiated, there was added 65 parts dimethyldichlorosilane. Thehydrolysis of this mixture was then carried out with ice water. Afterseparating the organic phase, it was dried, filtered and free ofsolvent. A red oil was left behind whose IR. is consistent with thefollowing formula:

0 H u//o Dal-01120119 C HgN O C 1141 0C5H5 EXAMPLE 5 There was added to9.4 parts ferrocene and 75 parts methylene chloride 19.8 partsmethyldichlorosilylpropylisocyanate with agitation commenced, there wasslowly added over a 1 /2 hour period 6.7 parts anhydrous aluminumchloride. A blood red complex developed. The reaction was allowed tostir at room temperature overnight. It was then decomposed with ice-H O.The organic phase separated, dried, stripped of solvent and purified bychromatography. A yellow solid was eluted with ethanol. It has avariable melting point. LR. showed it to be a mixture of cyclics of theformula,

EXAMPLE 6 The silylorganoferrocene of Example 1, which is 1,3-bis(ferrocenoylaminopropyl)tetramethyldisiloxane, was dispersed atdifferent concentrations in various samples of dimethylpolysiloxanefiuids of 1,000 and 5,000 centistokes viscosity. Thesilylorganometallocene was insoluble and when heated to C. a clearyellow solution was formed. On cooling the fluid became cloudy andmicroscopic examination showed it to be full of ribbon-like crystals.These crystals remained suspended in the fluid during freeze-thaw cyclesand did not settle out. The samples of the mixtures were tested byplacing 40 parts of the samples in a ml. beaker and placing the beakerin an oven maintained at 290 C. The time for gelation as well as theiron concentration and the silylorganometallocene concentrations in thefluid is set forth in Table I below.

TAB LE I Concentration of Fluid viscosity of Concentration ofsilylorganometal- Time to geladlmethylpolysiltron, percent by locene,percent tion at 200 0., ane,cs. weight by weight hours All of thesamples which exceeded a gelation time of 200 hours were placed in afluid clutch which was operated continuously for 200 hours. All thesefluid materials passed, thetest satisfactorily. I

. EXAMPLE 7 A silylcarbonylorganometallocene having the formula:

Hz was mixed with samples of dimethylpolysiloxanefluid of differentviscosities and at different concentrations. The mixtures were placed inan oven at 290 C. and the time to gelation recorded in TableII below.

TAB LE II Concentration of Fuid viscosity of silylcarbonylor- Time togeladimethylpolysiganometallocene. tion at 290 loxane, es. percent byweight 0., hours and (b) copolymers composed of structural units of theformula,

and at least one unit of (a) where R is a member selected from the classconsisting of monovalent hydrocarbon radicals, halogenated monovalenthydrocarbon radicals, cyano radicals, and fluoroalkyl radicals, (C Q)M(C Q is an organometallocene radical, R" is a radical selected fromthe class consisting of an arylene radical and an alkylene radical, Q ischemically bonded to a cyclopentadienyl radical and is a member selectedfrom the class consisting of hydrogen, a monovalent electron donatingorganic radical selected from the class consisting of aryl radicals,hydroxyaryl radicals, aliphatic radicals, cycloaliphatic radicals,carboxyaliphatic radicals, triorganosilyl radicals, and nitroaliphaticradicals, a monovalent electron withdrawing organic radical selectedfrom the class consisting of aliphatic aryl radicals, arylaryl radicals,carboxyaryl radicals, nitroaryl radicals, haloaryl radicals, andhaloaliphatic radicals, and mixtures thereof, M is a transition metal'bonded to two cyclopentadienyl radicals and selected from the classconsisting of titanium, vanadium, chromium, manganese, iron, cobalt,nickel, zirconium, columbium, molybdenum, technetium, ruthenium, rhodiumpalladium, hafnium, tantalum, tungsten, rhenium, osmium, iridium andplatinum, a is a whole number equal from 0 to 2, inclusive, and b is awhole number equal from 0 to 3, inclusive.

2. Organopolysiloxane polymers composed of structural units of theformula,

where R is a member selected from the class consisting of monovalent.hydrocarbon radicals, halogenated monovalent hydrocarbon radicals,cyanoalkyl radicals, and .fluoro' alkyl radicals, (C Q )M(C Q is anorganometallocene radical, R is a divalent radical selected from theclass consisting of arylene radicals and alkylene radicals, Q ischemically bonded to a cyclopentadienyl radical and is a member selectedfrom the class consisting of hydrogen, a monovalent electron donatingorganic radical selected from the class consisting of aryl radicals,hydroxyaryl radicals, cycloaliphatic radicals, carboxyaliphaticradicals, triorganosilyl radicals, and nitroaliphatic radicals and amonovalent electron withdrawing organic radical selected from the classconsisting of aliphaticaryl radicals, arylacyl radicals, carboxyarylradicals, nitroaryl radicals, haloaryl radicals, and haloaliphaticradicals, and mixtures thereof, M is a transition metal bonded to twocyclopentadienyl radicals, and selected from the class consisting oftitanium, vanadium, chromium, manganese, iron, cobalt, nickel,zirconium, columbium, molybdenum, technetium, ruthenium, rhodium,palladium, hafnium, tantalum, tungsten, rhenium, osmium, iridium andplatinum, and a is a whole number equal to from 1 to 2, inclusive.

3. The polymers of claim 1 wherein Q is hydrogen, and M is iron.

4. The polymers of claim 1 wherein R" is propylene and R is methyl.

5. The polymers of claim 2 wherein Q is hydrogen and M is iron.

6. The polymers of claim 5 wherein 'R" is propylene and R is methyl.

7. A disiloxane having the formula,

where R is a member selected from the class consisting of monovalenthydrocarbon radicals, halogenated monovalent hydrocarbon radicals,cyanoalkyl radicals, and fluoroalkyl radicals, (C Q )M(C Q is anorganometallocene radical, R" is a radical selected from the classconsisting of an arylene radical and alkylene radical, Q is chemicallybonded to a cyclopentadienyl radical and is a member selected from theclass consisting of hydrogen, a monovalent electron donating organicradical selected from the class consisting of aryl radicals, hydroxyarylradicals, aliphatic radicals, cycloaliphatic radicals, carboxyaliphaticradicals, triorganosilyl radicals, and nitroaliphatic radicals, and amonovalent electron withdrawing organic radical selected from the classconsisting of aliphaticaryl radicals, arylacyl radicals, carboxyarylradicals, nitroaryl radicals, haloaryl radicals, and haloaliphaticradicals, and and mixtures thereof, and M is a transition metal bondedto two cyclopentadienyl radicals, and selected from the class consistingof titanium, vanadium, chromium, manganese, iron, cobalt, nickel,zirconium, columbium, molybdenum, technetium, ruthenium, rhodium,palladium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, andplatinum.

8. The disiloxane of claim 7 wherein Q is hydrogen and M is iron.

9. The disiloxane of claim 8 wherein @R is methyl and R" is propylene.

10. A method for forming a compound of the formula,

by reacting an organometallocene (C Q )M(C Q H), with an isocyanatehalide of the formula,

in the presence of a catalyst selected from aluminum chloride, boronfluoride, phosphoric acid, hydrogen fluoride, zinc chloride and stannicchloride and then hydrolyzing the resulting product mixture where R is amember selected from the class consisting of monovalent hydrocarbonradicals, halogenated monovalent hydrocarbon radicals, cyanoalkylradicals and fluoroalkyl radicals, (C Q )M( C Q is an organometalloceneradical, R" isa radical selected from the class consisting of an aryleneradical and an alkylene radical, X is halogen, Q is chemically bonded toa cyclopentadienyl radical and is a member selected from the classconsisting, of hydrogen, a momovalent electron donating organic radicalselected from the class consisting of aryl radicals, hydroxyarylradicals, aliphatic radicals, cycloaliphatic radicals, carboxyaliphaticradicals, triorganosilyl radicals, and nitroaliphatic radicals, and amonovalent electron withdrawing organic radical selected from the classconsisting of aliphatic aryl radicals, arylacyl radicals, carboxyarylradicals, nitroaryl radicals, haloaryl radicals, and haloaliphaticradicals, and mixtures thereof, and M is a transition metal bonded totwo cyclopentadienyl radicals and selected from the class consisting oftitanium, vanadium, chromium, manganese, iron, cobalt, nickel,zirconium, columbium, molybdenum, technetium, ruthenium, rhodium,palladium, hafnium. tantalum, tungsten, rhenium, osmium, iridium andplatinum. 11. A method for forming a polymer of the formula,

H l sQa) aQ4) by reacting an organometallocene, (C Q )M(C Q H), with anisocyanate halide of the formula,

in the presence of a catalyst selected from aluminum chloride, boronfluoride, phosphoric acid, hydrogen fluoride acid, zinc chloride, andstannic chloride, and then hydrolyzing the resulting product mixturewhere R is a member selected from the class consisting of monovalenthydrocarbon radicals, halogenated monovalent hydrocarbon radicals,cyanoalkyl radicals, and fluoroalkyl radicals, (C Q,)M(C Q is anorganometallocene radical, R" is a radical selected from the classconsisting of an arylene radical and alkylene radical, Q is chemicallybonded to a cyclopentadienyl radical and is a radical selected from theclass consisting of hydrogen, a monovalent electron donating organicradical selected from the class consisting of aryl radicals, hydroxyarylradicals, aliphatic radicals, cycloaliphatic radicals, carboxyaliphaticradicals, triorganosilyl radicals, and nitroaliphatic radicals, and amonovalent electron withdrawing organic radical selected from the classconsisting of aliphatic aryl radicals, arylacyl radicals, carboxyarylradicals, nitroaryl radicals, haloaryl radicals, and haloaliphaticradicals, and mixtures thereof, M is a transition metal bonded to twocyclopentadienyl radicals and selected from the class consisting oftitanium, vanadium, chromium, manganese, iron, cobalt, nickel,zirconium, columbium, molybdenum, technetium, ruthenium,rhodium,,palladium, hafnium, tantalum, tungsten, rhenium, osmium,iridium and platinum and a is a whole number from 0 to 2, inclusive.

References Cited UNITED STATES PATENTS 3,324,157 6/1967 Wilkus et al260-439 3,326,952 6/ 1967 Wilkus et al 260-439 TOBIAS E. LEVOW, PrimaryExaminer A. P. DEMERS, Assistant Examiner US. Cl. X.R.

252-78; 260429.3, 429.5, 438.5 R, 439 CY

